FR2595367A1 - PROCESS FOR PREPARING MOLDED BODIES OF MODIFIED THERMOPLASTIC POLYAMIDES - Google Patents

Abstract

MOLDED BODIES, MANUFACTURED FROM THERMOPLASTIC POLYAMIDES WITH A PARTICULAR STRUCTURE, PRESENT BETTER MECHANICAL STRENGTH AND HIGH DIMENSIONAL STABILITY AT HOT, WHEN THE TREATMENT IS PERFORMED BY ADDING AN AGENT THAT CAUSES THE CHAIN BETWEEN THE RONDS. WATER. FOR THIS PURPOSE, BE ADDED TO THE DRY POLYAMIDE, WHICH PREFERABLY CONTAINS A HIGH CONCENTRATION IN THE AMINO GROUP (-NH, -NH-), BEFORE OR DURING THE TREATMENT, A MASTER MIXTURE CONSISTING OF A THERMOPLASTIC MATERIAL AS A SUPPORT AND D 'A SILANE THAT CAN REACT WITH POLYAMIDE AND HYDROLYZE QUICKLY WITH WATER. IN THE MELTED MASS, THE SILANE REACTS WITH THE POLYAMIDE, WHILE SIMULTANEOUSLY, THE MASTER MIXTURE SUPPORT DIVESTS FINELY IN THE POLYAMIDE OR EVEN DISSOLVES IN THE POLYAMIDE. THE MELTED MASS IS THEN TRANSFORMED, PREFERABLY ACCORDING TO AN INJECTION OR EXTRUSION MOLDING PROCESS, INTO A FINISHED PRODUCT READY FOR USE. THEREFORE, ALREADY IN CONTACT WITH THE NORMAL SURROUNDING ATMOSPHERE, THE POLYAMIDE FIXING THE HUMIDITY OF THE AIR, A REACTION OF JUNCTION OF POLYMERIC CHAIN, LEADS TO A HIGH UTILITY VALUE OF THE PRODUCT, IN THAT, FOR EXAMPLE, THE HOT DIMENSIONAL STABILITY OF IT IS HIGH.

Description

Process for the preparation of polyamide moldings

modified thermoplastics.

  Polyamides have proved to be very diverse building materials. At present, there are various main classes of polyamides which each have a

  interesting set of properties.

  Polyamide 6 and polyamide 6.6, as standard building materials made of polyamides, have relatively high softening temperature, but also a relatively high equilibrium water content, polyamides 11 and 12 having a high lower melting point, but also a significantly reduced equilibrium water content, and therefore better dimensional stability. The polyamides 6.9, 6.10, 6.12 and 6.13 occupy an intermediate position. Then come the purely amorphous polyamides, for example that consisting of trimethylhexanediamine and terephthalic acid, then polyamides which have

  actually a crystalline melting point, but also

  a high glass transition point, such as polyamide consisting of metaxylylenediamine and

adipic.

  In addition, there are currently many types of mixed polyamides or copolyamides in the

  preparation of which monomers of preferred

  and have found many possibilities of application, for example as glues for textiles, or glues for assembly. Despite the many possibilities of applications that have become possible thanks to these many types

  of polyamides, it is still apparent that

  for which current formulations of

polyamides are not enough.

  For example, for a modified resilient polyamide with a foreign polymer, the stiffness and

  the tensile strength decreases.

  By heating above the melting point, for example an insulating cable sheath or a purely linear polyamide cover is quickly suppressed by melting. By long-term friction contact with

  a rough surface, an object commonly used in polyamide

undergoing significant wear.

  In German Offenlegungsschrift No. 3,339,981 there is now described in general form a process which relates to the chemical fixation of a silane on the polyamide chain, and in which the silane structure then leads, under the action moisture, the formation of connection points of the polymer chain. Depending on the structure of the polyamide, as well as the nature and concentration of the silane, it is then advantageous to extend the chain or to form transverse crosslinking points. It is then possible to significantly improve

  properties such as resilience, dimensional stability,

  thermal resistance, and wear resistance by

friction.

  According to this general process, we obtain

  moldings having significantly improved properties.

  However, there is no method for their preparation

rational, safe and industrial.

  From the examples known from this publication, the polyamide granulate is first coated with a silane layer, and then completely loses its assayability. This is restored by adding a large amount of polyamide powder which forms a layer by sticking to the surface of the granulate. Grinding the resilient polyamide into the necessary powder is expensive and is only possible at low temperatures, for example in the presence of liquid nitrogen. It must then be dusted and dry completely. Since the polyamide in powder form has a very large surface, it occurs, already during

  short-term contact with the surrounding atmosphere

  In this way, the normal risk is that the silane will already produce crosslinking in the melting apparatus. Powders of a foreign nature, such as, for example, powdery processing aids, which can be used mainly to restore the drippability, also raise essentially the same problems, that is to say the risk of moisture and interfering substances being entrained in the reaction mixture. There is also a limit for the amount of silane that adheres to the surface of the aggregate and can be homogeneously distributed. In total, this two-step pretreatment process is long, uneconomical, and

  regularly linked to the risk of introducing moisture.

  The silane injection process in the polyamide melt certainly provides good results

  o the technical provisions exist and in

  extrusion, but it is not suitable for the treatment of

in injection molding.

  Extrusion treatment also has the disadvantage that expensive technical arrangements are required. This is how the silane must be

  injected very consistently and against a counter

  high pressure of the melt. Along the mixing unit between injection point and tool, high requirements are established to compensate for possible fluctuations in concentration and to distribute

  the silane sufficiently homogeneously.

  It has thus been found that a simple silane addition technique generally usable in injection molding and in the extrusion process would represent an essential technical advance for the production of silane.

efficient realization of the process.

  It has now been shown that the modification process

  polyamide with silanes can be carried out almost ideally by using

appropriate masterbatches.

  The invention therefore relates to a process for the preparation of molded bodies made of thermoplastic polyamides, which, in comparison with the starting polyamide materials, exhibit improved mechanical properties and high dimensional stability when hot, characterized in that it is added to the dry polyamide before treatment, a masterbatch which contains at least 5% by weight of a silane of formula I

I Y-Si- (A).

  Wherein n = 0, 1 or 2 Z is an inert organic residue Y is a divalent organic residue, bonded to the silicon atom, containing a functional group which reacts with amino groups and / or carboxyl groups and / or amide groups of the polyamide chain with formation of a chemical bond, and A is a hydrolyzable residue upon introduction of moisture, and in which residues appearing several times can also be bonded to one another, the mixture of polyamide and masterbatch are melted, the melt is thoroughly homogenized (mixed), and then converted, in accordance with the usual processes for the treatment of thermoplastics, into molded bodies, and these are subjected before use , at ambient humidity or at a

short time in the water.

  In order to carry out the process according to the invention in a simpb and practically satisfactory manner, it is established

  high requirements for support-

  master mix. Thus it must: have a good silane binding capacity, present at the concentrations used, sufficient compatibility with the polyamide, and distribute in the polyamide, when incorporated therein, without damaging important to the properties of the polyamide, do not destabilize the silane in its charged state with regard to its sensitivity to hydrolysis, as well as, in general, possess hydrophobic properties, so that there is no risk of introduction of moisture. In what follows, when speaking of silane, it is polyamide-reactive silane according to this invention, and in particular the following types of silane: epoxy-silane of the formula ## STR2 ## -CH 2 -O- (CH 2) 3-Si (OCH 3) 3 II and isocyanatosilane of formula O = C = N (CH 2) 3 Si (OC 2 H 5) 3 III Numerous tests have shown that there are several techniques for the preparation of a appropriate masterbatch. Technique 1: A polyolefin melt is directly charged with silane and the silane-containing melt is drawn into a pudding, the pellet is ground into a granulate, and the pellet is carefully dried. Technique 2: If the support material is capable of swelling in the presence of silane, it is then, for example in the form of lumps, grains, or coarse powder, put directly in contact with the amount of silane which is directly attached. The support must then remain naturally able to drain, that is to say that

  must not show any adhesion.

  Technique 3 To a thermoplastic material, which is an open vacuole foam but is not liable to swell in the presence of silane, is added

  at most the very amount of silane that ensures the filling

  wise vacuoles but that does not harm so

  essential to the dewatering capacity of the product.

  We generally use technique 1 when the

  Thermoplastic material does not spontaneously fix the silane.

  For this process, for example, the polymer called LLDPE (linear low density polyethylene), ethylene / propylene copolymers (EP gum), elastomers known as EPDM, low glass transition point copolyolefins which can be grafted to a low degree, for example with maleic anhydride, or mixtures of these polymers. Products having a good flowability, for example products having a "melt index", are suitable.

  determined according to IS0 R 292, of 5 and more.

  For the practical realization of the process, the products are melted for example in a two-shaft mixer, say in a so-called two-disc mixer, for example a ZSK-30 machine from the firm "Werner and Pfleiderer", Stuttgart. Through a degassing tubing, the silane is then continuously introduced.

  in the polymer melt in a weighted proportion

  preset. It shall be determined during a pre-test that the maximum silane

  the melt. For continuous silane dosing,

  for example, electronically controlled peristaltic pumps with 6 or 8 elements, the silane being brought without pressure to the surface of the melt of the

  polymer and then incorporated by kneading and dissolved.

  The resulting extrusion strand can be cooled in a water bath, as long as it can be continuously ground into a granulate. However, the time of contact with water must be limited to such an extent that it only has the necessary cooling function and is vaporised again between the outlet of the cooling tank and the cooling device. cutting. Transport from the extruder to the granulator can be carried out on a cooling strip,

  for example a steel strip cooled with water.

  Technique 2 is suitable in the case where the thermoplastic spontaneously fixed the silane. This technique is extraordinarily simple and well suited

  for the practical implementation of the method. A simplification

  The important technical requirement lies in the fact that thermoplastics have been found which spontaneously and in a short time fix large quantities of silane without sticking, which can be well incorporated in the polyamide in the charged form in siland, releasing the silane of such so that it can react with the polyamide, and which then exert little influence on the

  transformability and mechanical behavior of polyamide.

  As polymers that can be used in accordance

  According to technique 2, block polymers having a rigid sequence and an elastomeric segment are suitable. The rigid block is then made up, for example, of polystyrene, and the elastomer segment, for example of polybutadiene, of polyisoprene, or of a saturated sequence, that is to say not containing a double bond, for example of ethylene copolymers. / butene or ethylene / propylene. The elastomeric sequence can also be a mixture of different sequence structures. The ratio of rigid sequences to elastomeric sequences can vary within wide limits. However, it is preferred to use triblock polymers having a proportion of elastomer blocks of at least 50%, in particular 60 to 75%, since it is the elastomeric block which is responsible for the silane binding. Styrene / ethylene / butene block polymer with a proportion of 70% by weight of ethylene / butene

  fixed without sticking more than its own weight of silane.

  These block polymers can be introduced in the form of lumps, granules, grains, or powders. Grains having an average diameter of about 0.1-0.2 mm are well suited. They do not make dust, they fix the silane in a short time, and they adhere well to the surface of the polyamide granulate; it is then formed, already after a mixing time of a few minutes, a homogeneous mixture between such

masterbatch and polyamide.

  In general, a master-support mixture of this nature is loaded for example with more than 20% by weight of silane. Masterbatches containing about 50%

  by weight of silane are particularly suitable.

  If the polyamide is processed together with such a masterbatch, then the ready-to-use finished product contains very little foreign polymer, and the basic properties of the polyamide remain.

to a very large extent.

  The general method according to technique 2 is therefore very simple and is no longer described.

  especially later in the examples. Through

  With the aid of a mixture of light masterbatch mixtures, for example poly (styrene / ethylene / butene / styrene) triblock polymerized grains, the silane is added and the mixture is briefly homogenized by shaking. After a brief rest period, for example minutes, the silane is fixed. A predetermined amount of the masterbatch, for example 2 to 3% by weight, is then added to the dry polyamide aggregate and blended until the masterbatch is homogeneously distributed over the aggregate. This is so after a few minutes. The grains then adhere well to the surface of the granulate. The mixture can then be stored for a certain time or transformed directly. The

  only condition is the eviction of moisture.

  Technique 3 is based on the targeted use of open vacuole polymer foam, which absorbs

  spontaneously liquids through the forces of capllarity.

  Such polymer systems are for example described in

  "Kunststoffe" 71, No. 3, pages 183-184 and DE-P-27 37 745.

  Polymers having such microporous structures are for example prepared from various types of polyethylene, polypropylene, polycarbonate, but also polyamides 11, 12, 6, and 6.6. The pore volume is 50 to 85%, and the pore diameter is in the range of 0.1 to 10 microns. These microporous polymers can set up to three times their own weight of silane. With this, the relative influence of a

  possible residual moisture is comparatively low.

  As a masterbatch for the treatment of polyamides, particularly suitable are medium-low viscosity nylon-11 and microporous nylon-12 grains. These types of nylon have the lowest capacity for moisture fixation among linear polyamides, they melt well during their processing,

  and they dissolve well, at concentrations of

  cation, in all polyamides, so that in the final product, in virtually all

  cases, there is a homogeneous polyamide phase.

  The technique 3 generally represents a particularly advantageous mode of use of the process. The only drawback is the relatively high cost of

  process for the preparation of microporous polymer systems.

  Microporous polypropylene and polyamide 12 spontaneously fix about three times their own weight of silane. The main use of this type of master mix is the process according to the

technical 2.

  For the treatment corresponding to the process according to the invention, all the polyamides that can be

  Thermoplastic work can be used.

  In particular, it has proved advantageous to use polyamides having known and clearly defined reactive groups. The amino groups were

  revealed to be especially advantageous.

  If a search for a largely linear extension of the chains with the least possible cross-linking points, then polymer chains having polyamide-NH-R groups at the end of the chain are especially advantageous. Chain ends of this nature can only react with one silane each, whereby it is advantageously formed, during conditioning, junction points between two

  polyamide chains, located at the ends of these chains.

  If it is proposed to construct a three-dimensional network, then polymer chains having terminal-NH 2 groups are used, as well as, according to

  the desired degree of crosslinking, additional -NH- groups

  in the chain. The concentration of -NH2 and -NH- groups, expressed for example as microequivalents (-NH- + -NH2) / g, in the polyamide melt is a direct measure of the possible crosslinking density if a silane is used. reagent to amines. If the polyamide chains are structured in such a way that the amine functional groups are exclusively at the end of the chain in the form of an NH 2 group, it is thus possible, with a short-chain polyamide, to achieve a desired higher transverse crosslinking density than

  for medium and high viscosity polyamides.

  Cross-linking is essential

  the fact that two isocyanate or epoxy groups can be attached by adding, almost equivalently, to the -NH 2 groups, whereby it is first formed, for example for a silane corresponding to the formula I, the following structure: H 2 -CH.CH 2 O. (CH 2) 3. If (OCH3) 3 OH Polyamide chain -N CH2-OH.CH2.0 (CH2) 3 'Si (OCH3) 3 The following figure shows a domain of polyamide chain joining, o various kinds of junction between

  chains and ramificatiors are schematically represented.

  R y represents the intermediate link (-O- (CH2) 3-).

  ## STR2 ## ## STR2 ## ## STR2 ## where ## STR2 ## (Apolyide CH 2 CH 2 OH (OH) -si O (HO) 2-ii RI CH'OH CR2 IN POLYamide I chain

- R.

  CH2 CH-OH! R1 HO-Si-O-Si-R'CH'OH O (B) Si .- (OH) E 2 R CH-OH H poly (C) HN polyamido (D) (A) represents chain branches which are formed by additive attachment of two molecules of

silane on a -NH2 group.

  (B) shows the rarer case o chain branching

  intervenes at the level of a silicon atom.

  (C) shows the case where a single molecule of silane was

  available for reaction with the -NH2 group.

  (D) is the structure that is formed when an amino group

  secondary is at the end of the chain. The ramifica-

  The chain ratio corresponding to (A) is clearly

tagger with respect to (B).

  Since the type and concentration of groups

  in the polyamide are given by the

  polymerization range (type and concentration of the chain regulator) and can also be easily controlled analytically, it is also easy to calculate the appropriate concentration.

  silane for a silane reactive with amines.

  The chemical modification of the polyamides can therefore be used very appropriately and adapted to the

practical requirements.

  Thus, for a chain-terminated polyamide -NH 2, having, for example, 40 / ueq / g (NH 2), and when the silane corresponding to formula I (M = 236.4) is used, the maximum amount of silane reactant is 40.2.0.2364.1 = 18.9 g of silane per kg of polyamide. The process is not limited to pure polyamides, but is also suitable in many cases for alloys or mixtures of polyamides in which at least one component is a polyamide and / or the other components may be inert to silane screw, but also present reactive positions

vis-à-vis the silane.

  Examples of the alloy components are: the known types of polyethylene, for example ethylene-based mixed ethylene polymers with butyl acrylate and vinyl acetate, but also to a limited extent , mixed polymerisates of olefins grafted (for example

with maleic anhydride).

  Components of reactive alloys vis-à-vis

  of silane are, inter alia, the polyesters

  plastics, mixed polymers of ethylene and acrylic acid, polyether-terminated polyethers, or mixed polymers of ethylene and alcohol

vinyl.

  Moreover, it is also possible to treat

  with the polyamide and the masterbatch, which is

  called PEX (chemically crosslinkable polyethylene).

  The polyamide and the polyethylene then form, under the action of moisture, networks in the form of separate phases. However, there is also a chemical bond at the separation surface because the silane attached to the surface of the polyamide reacts with the silane attached to the surface of the polyethylene to form an Si-O-Si- bridge. The polyamide matrix then facilitates the transport of moisture to the dispersed polyethylene phase. Depending on the nature of the processing of the starting materials, different demands are placed on the machines, and bodies can be obtained.

  molded, that is to say finished products, different.

  Since in general, in the master batch process, the aggregate and the masterbatch are premixed prior to processing, this is suitable for all thermoplastic processing processes

  polyamide and processed polyamide formulations

thermoplastic mables.

  It is necessary that in the melt state, before the shaping process, there is an intimate mixing of the melt, and that the silane can be distributed

homogeneously.

  For all processing devices, the feed device, for example the hopper, must be in such a way that the mixture of polyamide and masterbatch that is present can not fix moisture. This can be achieved with simple means, for example a tightly sealed lid combined with a dry gas sweep. A slight heating of the load may represent a

effective protection measure.

  In injection molding, screw injection presses are thus required which comprise a powerful three-zone screw. Under certain conditions, it is possible to use a degassing plastification unit, but on the other hand, piston injection presses do not

are not appropriate.

  During the melting process, the mixture of polyamide and masterbatch must be homogenized vigorously. During the duration of the injection, the maintenance pressure, and the cooling time, it does not occur, as usual, melting the mixture of aggregates and masterbatch. When injecting silane, the injection process should be performed in absolute synchronization with the fixing process on the aggregate, and so should not appear in the finished part, any variation,

  for example with regard to the degree of crosslinking.

  A solution corresponding to this problem would represent an important technical cost. In the master batch process according to the invention, such problems do not occur.

do not pose, however.

  Problems arise mainly from

  identical way when blowing hollow bodies.

  In extrusion and blowing process

  by extrusion, the granulate is melted continuously.

  Thus, both the master batch process and the process for direct injection of the silane into the polymer melt are suitable. In both cases, an efficient mixing device is necessary. Direct injection, however, requires many adjustments and technical provisions, which are completely removed in the master batch process. This method is therefore advantageous for universal use, and also when

uses extrusion.

  The molecular structure of a polyamide finished part is strongly influenced by the process according to the invention. From a linear chain structure, we reach, through branched chains with high molecular weight, structures

totally reticulated.

  The modification of the properties concerning the mechanical and thermal resistance, and therefore the possibilities of application, are closely related to one another.

  with others.The modified polyamide parts comply with

  Thus, according to the invention, better mechanical properties, higher hardness and abrasion resistance, as well as better dimensional stability, are required.

the melting point of the polyamide.

  Interesting applications also result from the appearance of the so-called memory effect, that is, the shape of cross-linked, injection-molded parts can be modified after they have been heated up. above their melting point,

  and freeze them in their new form by cooling

  below their melting point. After a new heating above their melting point, the pieces change shape again to return to that given initially. For example, it is possible to manufacture, for example, well-sealed coupling pieces of tubes or cables, which contract at the connection point of the tubes or cables and provide

  thus a very good seal.

  The following examples serve to further illustrate the invention. We first describe, in

  Examples 1, 2 and 3, the different methods of preparing

  ration of the masterbatch. Tables 1, 2 and 3 con-

  respectively the compositions of the corresponding masterbatches. The polymers used for carrying out the process according to the invention are mentioned in Table 4.

  manufacture of the samples necessary for the

  cation of the process. The results of the tests are collected

in Tables 5 to 14.

  1. Preparation of a master batch by introducing a determined amount of silane into a thermoplastic melt A two-axis mixer ZSK 30, from the firm

  Werner & Pfleiderer, Stuttgart, is stocked

  medium of a vibrating hopper, with the granulate

master mix.

  In the region where there is a homogeneous melt, the silane is brought into the melt in a continuous liquid stream through an open degassing tubing, and the silane is fixed by

the melt in motion.

  The master melt-mix is removed as a roll, and briefly passed through a water bath for cooling. The boudin, still hot, containing no more surface water, is then

  granulated and stored in a well-closed container.

  2. Preparation of master batch by direct fixing of silane by thermoplastics

  Direct fixation means here that the thermo-

  plastic absorbs spontaneously liquid silane when

contact with this one.

  For this master batch preparation mode, the silane is first distributed as finely as possible to the surface of the support. This can for example be achieved by sputtering the silane and subsequent mixtures. The mixture, at first moist and sticky, generally becomes once again after absorption

well suited to dripping.

  For example, based on the weight of the polymer, a finely pulverized, MBS-type shell-and-core polymer with about 58% by weight of polybutadiene, fixed 50% type 1 silane, and a polymer of the same type with about 46% by weight of polybutadiene, fixed at 33%; a finely pulverized shell-and-core polymer of the ABS type, with 42% by weight of polybutadiene, fixed at 33%, and a shell-and-core polymer, finely

  pulverized, pure acrylate type, fixed 50%.

  3. Preparation of master batch by fixing the silane with an open-celled polymer foam To prepare the corresponding masterbatch, the following can be carried out, for example: - The silane is uniformly sprayed on a porous granular polymer which is well adapted to draining, while stirring continuously this one. Already after a short contact time, the silane is absorbed and the

  polymerisate is again able to drain.

  The polymerisates used for the tests have a free pore volume of 50-85%, for a pore diameter of 0.1-10p, and are generally capable of setting in a short time 50-75% by weight.

  silane (relative to the sum of the products).

  To test the process of the invention, masterbatches, such as those shown in Tables 1, 2 and 3, were mixed with various polyamides, in the absence of moisture, and tested under

form of samplers or tubes.

  The polyamides used are collected in

the following table 4.

  Polyamide 12 was prepared according to the state

  known in the art, by respecting a phase of com-

  pressure in order to open the lactam ring. The preparation of polyamide 6 is also part of the state of the art. Polyamide 6/1 was prepared in a so-called pre-condensation pipe, closed, by stabilizing the chains with water, and 6/2 polyamide in a 50 liter test autoclave by adding diaminohexane as a chain regulator. Transparent polyamide GRILAMID TR 55 has been prepared

  according to Example 10 of DE-P-2 642 244. The preparation of

  The polyamide MXD.6 is described in European Patent Application No. 71 000, but it can also be carried out by mixing all the monomers in one step while maintaining a compression phase. The other process steps then correspond to the known stage of the art, as they are also usual for the preparation, for example polyamide 6.9 or

polyamide 6.12.

Table 1:

  Preparation of a master batch by direct introduction of a determined quantity of silane into a thermoplastic melt. All the copolymers containing silane in the levels described have no exudation

  silane, and are well suited to dripping.

  Note: melting index determined at 190 C and under a

load of 2.16 kg according to ISO R 292.

COMPOSITION 'MAEMPDE FABRICA & TIQI ,:

  Material -portportSilvertaste for the material-

  For example, the following can be obtained from the following sources: Melamine Pressing Barrier C NM LLDPE, MI25II 5 150 29 11 156 Copolymer 2 .. il 9 150 27.5 10 153 ethylene + octene 3 _ I 10. 150 25 6 168 thyne octane _ À- HZ - 6II- <7. ## STR1 ## , AE) 9 Alliaic of 51 clil10 150 38 1O 176 The copol> yire EP +. The composition of the present invention is that of the maleic anhydride / about 0.3% substituted with maleic anhydride and the 50M alloy of 150/155. The EP LL + copolymer (see test is grafted with 4). 50% of CHF 0.3%

_ ethvlyn.ro, yl _.

1.Wr / sat of ar.ydrde

fur, lfe / ', y ,,, ..

Table 2:

  Master batch preparation by direct attachment of the

silane by the support.

  Notes: - Form of support material G = granulate / Gru = lumps, small soft grains, - suitable for dripping = approx. 1% approx. 2-10 mm / P.G. = lumpy, 95% wt, 0 0.2-3 mm

silane fixation,

  advantageously with microtalc - S = styrene, EB = ethylenebutene, EVA = ethylene / acetate

of vinyl.

  Time CQMPOSITION enecssa Appearance of the necessary z Matrau-support to fixatioi master mix Material-support t fac dsl S -rdu silane

Type - (h.

  AT. Type Form Type 12 VA-TerpolymerCXA 1025 G Il 10 approx. 2.5 dough on the dough 13 G II 20 approx. 4.0 suitable for 6gouttaae 14 ... G III 10 approx. 3.0 Suitable for drainage (Du Pont) "- '" G III approx. 5.0 suitable for spraying 16> SBS, 28% SGru 20 approx. 1.5 to aegottaca 17. Gru IV 15 approx. 0.5 drip drip 18 # (S <FT ') Gru IXI 15 approx. 0.5 lpte at 3gouttag 19 SBS SBS, 28% SP (II 50 nv 2 Mnnnc a V &, oettaae Pole.nrc sCquencé sas, 33. SPG 50 approx 10 min tA .. & oouLtace 21 Sequence SES Polymer, 29% S PG XI 50 ~ 10 min-2 C-Cluster 22 Polymer SES, 29% S PC III 50 10 tin-ate-ag 23 - PG IV 50 10 M-In. Suitable for aerating 24 'PG V 50 10 Min au auttee PG VI 50 10 Min dewatering 26 DG VII 50 10 Min pourable 27 "PC-I 60 10 Min. adhesion tendency 26, tS T) PG lX 65 10 kin. dhérence desg / in

Table 3:

  Preparation of master batch by charge with silane

  of a polymeric support with open vacuoles.

  Temos CO.MPOSITION necessary Aspect of lacfixatirene tr z Supportsupport - Silane Tne Ju silane Type, 29 ke of polyoropyrene ricropore.50 vx v

14 E 04

II 75 'I

31 - "IV 50 4EO

  32 - - V 50 v 0.3> 33. Vi 50 O c 34 "IIf 50. 5 i 35 - - II. 75 flocculating o or 36 polyamide 12 micropore <T 50 cori 29-34 medium viscosity v 37! " ii% 50 c o. weapon 29-34 3tII6 0 floculatoni

38 60 _______ ,, ._ J ....,

  In Tables 1 to 3: Silane type I Silane type III Silane type IV Silane type V Silane type VI o C-CH-CH-O- (CH) Si (OCH)

2 \ 2- 23 3 3

* O =. OCN (CH2) 3Si (OC2H5) 3

2 3 2 (0H3

= C C (CH) Si (OCH3)

232 3 3

  -CH2 = C'CO'O (CH2) 3si ((OC3) 3 CH3 = CH2 = C-CO-O (CH3) 3Si (OC2H40CH3) 3 CH3 H2N (CH2) 3Si (oC2H5) 3 = Silane of type VII

Table 4:

  Composition of the Polymerisates Used T-PIoISAT E PAR Type of Ie. N C Type of group a

_ PA <1> (2) (3) (4)

  Po 1 PA 12 1.57 120 16 -N for injectian injection, low vison Po 2 PA 12 1.69 90 12 -NE2 Tye ion by binding, vsmoiXt..e Po 3 PA r2 1.67 104 -NF: i # Po 4 PA 12 1.58 390 -NH-zFe for Injection Molding, Low Visibility Po 5 PA 12 1.93 68 14 -NE2 ype for ectio molding and for

Po 6 PA 12 1.95 256 11 -NH-

Po 7 PA 12 1.91 166.16 -NU- #

Po 8 PA 12 2.07 109 21 -NB-

PO 9 PA 12 2.00 100 35 -NER + -NE-

  w f Po 10 PA 12 1.94 63 31 -NR PolYen W CARARCI STIGC OF PA NOTES No TPAe l nrel. NC Qfondu (1) (2) (3) (4) Pa-s (S) Po 11l PA 6 1.61 120 20 80 270 PA 6 low visosit-asse for injection molding (PA 6/2) Po 12 PA. 6 1.84 53 57 200 270 PA 6 of pure Royce-rasse visosifte injection molding (PA 6/1) Po 13 PA 6 1.90 -50 50 300 270 PA 6 of medium-viscosity viscosity for injection molding (PA 6/1)

  Po 14 TR 55 1.55 70 50 1i7o00 270 Polyamide prepared by injection

  t / no transparent, with a glass transition point of 155 C

  Po 15.XDA-6 1.60 89 62 100 270 Xt8cdf ffu polY.nide casti

Q 21, "and acid

__ipe2T2-

  Notes to Table 4: (1) = relative viscosity in solution, measured on a 0.5% solution of the polymer in m-cresol, at 20 ° C, according to DIN 51 562 (2) = concentration in amino groups, determined by analytical expressed as total microequivalents of amino groups per gram of polymer. The dosage

  can be carried out for example by way of

  metric with perchloric acid in a mixture of m-cresol and isopropanol (see Metrohm Bulletin No. 68 d, Herisau, CH) (3) = analytically determined carboxyl group concentration, expressed as microequivalents of carboxyl groups per gram of polymer. The dosage can be carried out for example in benzyl alcohol, at 100 ° C., with a solution of KOH in benzyl alcohol, with visual detection of the change in phenolphthalein (4) = nature of the amine functional groups obtained in the polymer. This is given by the adjuvants of polymerization and by the nature of the regulators

of chain length.

  In particular, we have chosen, for: -NH2: diaminohexane

  -NH-: diethylenetriamine or dihexamene

  thylenetriamine, with in each case azelaqual acid -NHR: 4-amino-2,2,6,6-tetramethylpiperidine, in combination with azelaic acid In addition, in all tables: PA means "polyamide" Po means "polymerization" MB means "masterbatch" 3. Production and evaluation of the samples To test the process, samples were prepared from the polymers Po 1 - Po 15, combined with a selected masterbatch, which is then generally calls for standardized small test specimens, according to DIN 53 453, and has tested their resilience to the notch as well as their dimensional stability over the point of

normal fusion of polyamides.

  In order to test the process otherwise, a tube having the dimensions indicated in the tables was manufactured on a measuring extruder of the firm Schwabenthan, Berlin, Type SM 30 U, for a temperature of the mass ranging from 190 to 220.degree. , and we tested

  especially their dimensional stability in the molten state.

  The results are collated in the tables at 14 with a short comment. The small standard test specimens (KDB) measuring 60x6x4 mm were manufactured on a

  injection molding of the firm Netstal, CH-Nieder-

  urnen, Neomat type N 110/565. The machine is equipped with a fusion extruder that effectively homogenizes the melt. The fusion parameters, such as the temperature profile of the fusion screw, the number of turns, etc., are adapted in each case as best as possible

polyamide used.

  To test the dimensional stability above the normal melting point of the polyamide, the KDBs are subjected, on a metal plate, for the time indicated in the tables, in the test column, to the corresponding temperature stress, for example, in Table 5, for 15 minutes, at a temperature of 230 C. In the following columns "appreciation", the signs have the following meanings: -: no dimensional stability, the material flows into a pool of melt +: the form the base of the sample remains maintained, the vertices and edges are rounded +: the shape of the sample remains maintained. Vertices and ridges are at most rounded to a very small extent. We can still define intermediate states: - +: KDB strongly deformed, trend detectable flow. + ±: for a well-maintained basic form, the vertices

  and the edges are a little rounded.

  In Table 5 are collected tests relating to polyamide 12 types with medium and low viscosity. The masterbatches used each contain type 2 silane, and are added so that the mixtures of tests 40, 41, 43 and 44 each contain 1.2% by weight of silane, and that of

  the test 42, 1.0% by weight of silane.

  The dimensional stability is in all cases improved compared to the test 39 (where there is no addition of silane). The resilience to the notch is in all cases significantly greater than the value obtained for the non-comparison material.

modified 39.

  For the tests corresponding to Table 6, types of high viscosity polyamide 12 were used, polymers 6 and 7 having, in addition to end groups -NH 2, -NH- functional groups in the polymer chain. Tests 45 and 53 are comparative examples corresponding to the polymerisate without the addition of a masterbatch. In all tests, the dimensional stability in the molten state is significantly improved. Resilience at the notch also increases sharply. A star (*) means that only

  part of the test piece is broken.

  For the tests corresponding to Table 7, a low-viscosity starting material was used again, and it was combined with the master mixtures of types and 11. Tests No. 58, corresponding to the pure starting material, as well as No. 65 , are comparison tests. Two stars (*) mean that the base component of the masterbatch 10 has been added to the base material, but without silane loading. The results of the dimensional stability tests, as well as the measurement of the notch resistance, show

  again clearly the influence of the reactions of

stringing chains.

  In the tests of Table 8, various polyamide-based material polymers 12 have been treated beforehand, each with the master batch 10. With the exception of Po 3, they are all high-viscosity materials. With the master mix concentration

  used, only test 67 gives dimensional stability.

  insufficient and a small increase in resilience to the notch. All the other tests present, for an assessment + dimensional stability, very high values of the resilience

  at the cut. O.B. then means "without breaking", that is

  that is, none of the moldings tested are broken.

  Tests 72 to 77 show that, from 7% by weight

  of master batch addition 9, the dimensional stability

  and resilience to the notch do not vary

more significantly.

  Tests 76 and 77 show that different types of polyamide 12, in the form of a mixture of aggregates, can also be treated successfully according to

  the process according to the invention.

  The tests in Table 9 are based again on low viscosity polymer 1. The masterbatches are added such that the test moldings 78 to 83 each contain about 1% by weight of type 2 silane, and the moldings of

  Trials 84 to 87 each contain 1.5% by weight.

  There is a definite correlation between dimensional stability and the amount of silane added. The resilience to the notch is also significantly increased, but it varies at the same time, which can be attributed to the secondary influence of the material of

base of the master mix.

  In the tests of Table 10, the polymers 9 and 10 are treated with small amounts added of the masterbatches 19 and 22. The tests 88, 89 and 94 are again comparative tests. Tests 88 and 94 correspond to the pure polymerisates. For Run 89, 2% of the base material of the masterbatch was added without silane loading. The experiment again shows an increase in the dimensional stability when hot,

  as well as improvements in notch resilience.

  Table 11 shows the tests carried out with Po 14 (transparent polyamide) as well as with polyamide 6 and polyamide MXD.6. From a concentration defined in the masterbatch and therefore in silane, the dimensional stability when hot is again improved. The notch resilience of these products, which are in themselves rigid and not very resistant to shocks, is also increased by the reactions of

chain connection.

  Table 12 contains tests in which one directly transforms into test pieces, by adding a master mix according to the invention, a mixture of aggregates of a type of polyamide 12 with high viscosity and a type of polyamide 12 with low viscosity with what is called a HDPEX, type 7121-10, from the firm Asea Kabel, Stockholm. The resilience to the notch is then determined after conditioning in water and drying (column 1), as well as after conditioning in water and subsequent storage for 1 day

(column 2).

  Variants indicated by * are comparison tests. In the test tubes, the polyethylene is present in finely divided form. Whereas during a net bending immediately after the extrusion, it appears effects of delamination, these effects

  are only weakly detectable after

  in water and subsequent drying. It can therefore be assumed that chemical bonds, in the form of SiSi bridges, are also established on the surfaces

phase boundaries.

  Resilience is again significantly increased compared to non-silane containing products.

  Table 13 gathers manufacturers' tests

  cation of 8xl mm tubes. For this purpose, the NH 2-terminated polymerization was used, and the

  polymerisate 8 containing -NH- functional groups.

  The tubes are manufactured on a "Schwabenthan" test extruder. In the "tube" column, a represents the outside diameter of the tube, and the thickness of its walls. In the "manufacturing" column,

  1 represents the rotational speed of the screw of the former

  2, and 3 represent respectively the first and last (on the die side) adjusted temperatures of the heating zones of the cylinder, and 4 represents the drawing speed of the tube. For this test, an open and unheated feed hopper was used so that the polyamide could fix a little moisture before treatment. It then followed, already during the manufacture of the tube, a partial formation of bridges

-Si-O-Si- in the melt.

  By extrusion of tubes, smooth tubes whose form is absolutely stable when heated above the melting point are formed from the polymer (end groups -NH 2 alone).

  polyamide. From the polymerization 8, we form

  rough surface tubes which, when heated correspondingly, do not form any melt puddle, but undergo a sharp contraction in length (L-contraction). This is closely related to what is called the memory effect. The polyamide melt, already having numerous cross-linking points, is stretched between the die and the mold, this stretched state finally being fixed by cooling. The non state

  stretched is then taken again during a new merger.

  This effect does not appear to be extensive for a polyamide with end groups -NH 2, where chain extension reactions with

silane.

  Tests 129 and 130 concern the manufacture of tubes from a polymerizate-like polymer, but with a somewhat shorter chain length (93 meq / kg NH 2). By adding masterbatches based on Silane II and Silane III, it is possible to

  in each case produce tubes of satisfactory quality

  having a good dimensional stability, and having no contraction effect when heated above the normal melting point of the polyamide. For the tests corresponding to Table 14,

  Polymerisates were used, in each case carefully

  dried, Po 5 (amino terminal groups), Po 9 (Nsec in the chain and at the end of the chain), as well as Po 10 (Nsec at the end of the chain), and the extruder was fitted with a closed hopper with dry nitrogen sweep. Thanks to the careful elimination of moisture, we obtain in

  each case tubes having a beautiful smooth surface.

  The result of the dimensional stability test at 230 C can be explained from the different structures of polyamide chains. For ends of chains -NH2, as well as, in particular, for chains with -NH- chains, there necessarily appear points of transversal connection between the polymer chains. For polymer chains advantageously having only one end-chain reactive hydrogen atom (-NHR), the silane coupling reaction produces to a large extent a linear chain elongation, the viscosity at the end of the chain. increased molten state

  then purely and simply in the first place. The decrease

  length (L-contraction) does not appear since the granulate is completely dry and

  therefore produces no partial reaction in the extruder.

Table 5:

SAMPLE COMPOSITION T E S T

  Essar ssl PA MrB Hot Fabricaton Densional Feedability R6sillene to N N P. Type Fabrica to. 3 hot 1 'size TEMARQUFS _ o No% Weight Apparatus Coedition. T (mDC Mit # 39 ['o 1- KDB3Neomato o 230 1 d. 2.0Creative Trial

N 110/565,

S 12,, 2.

41 3. * 8.

. 3- ^

  42 "301.33 t n + 0 S.3 t ,, 0+ ml

i0.

.3 '., -,, 5.3

4 3ro 35 12 "". "9

. C *. at.

441ro4 ,. Ol .... o,.,., + _ N 12.6.

OQ ...

, .....

  ## EQU1 ## where ## EQU1 ## This is the case in which I am kj / m2

REMARK ES

  -t ------ * U --- * -.-----. I ------- J I I _____ I t Il Il 1 5 4 - 4- Cond. It is possible that it is possible to test it.

56 2O 5 3 110 KDB 230 15 * - 54

57 "5 10 ..... _ (A)

y_ NO t '> LAl m%

Table 6:

! COMPOSITION

  SAMPLE H T% 1 di Type Po 6 Manufacture I lt, .. - Ist it i% Itaa, li Iva -InnltNn ,,, I.i.Z f7'Z.I Apparatus ICorn.ition :. T (* CI 1 t tMin) Neomat '

N 110/565

  4 5 o a. gold:. KDD He He He KDB I - II o 1.13 ii I! ii tl 2 30 Il Il Po 7 ----- --- - t L i i i II It r, Table 7:% o rl OL tu (% 1.

COMP. '

com4tol, Essay _

N P

No. 58 Po 1 59. "Ln 60" 'm

Table 8

COMPOSITION EC'ANTILLON T F S T

  ## EQU1 ## where: ## EQU1 ##, ## EQU1 ## (IC (here) t (nlpp'.tI atkJ / m2 66 Po 5 10 7 KOB Neomat '230 15 + cond.oB

67 * PO 3 "N 110/565 6

  Po 6 7: "" "" "40 69 Po 7 O." O Po 9 t 62 71 Po 7 11 "" "" + 35 72 Po 8 9 7. ItDR'Neonmat 230 15 SS cond.

N. 110/565

73 "" '* S I + 60

74 "9" 55

74 l.1 .. + - ss * 10 * e "53

76 PO 1 9 i. "+" 73tP01 +.

  + 8 70o.Po 8 77 Po .. .. o 50% Po 5 + + 8 :. 501 Po 8 N. 0% 0 t0 CM

Table 9

  XOSITIONECATIL T E S T E S T Density StahilfItOr. essiúence 'Sin

  N p &. % 3 .... Type A hot notch add &.

  N N. % weight Aaril Cnditions T ('C) t (Mln) Aupr.State kJ / m2% at 78 Po 1. - - KDB Neomat 230 15 - 2si. N llO / 565 t | t. .N 110/565

79 "30 1.3" "" 1/6 ± '5.8 0.9.75

19.

19 2.0 gr.l.l + _ 5.9 1.00

81! "13 5.0" 13 1.00

82 "20 2 .. 4.5 1.00

"e 6 -.0 1.00

03 "21 2.0 + 6.0 1.

M 84., O 2.0 ". O" 7.1 1.50

"19 3.0 ... .3 1.50

86 "20 e .. + 7.1 1.50

87 "1 6.7 1.50

"'0% 0 Do not

Table 10:

SAMPLE COMPOSITION T E S T

  EIsSai --Sij EPAiP MD Manufacturingi lhl> l. t diinin Roni; = ee ESA No To 'Type t:' II ten, E At U5

IO 9. - KD2, - -

  N Born Type Appartil Itin foct (Iomat T! CtMl y00Po 9 _ DB Neomat f 2301S - 5. 5Cararat1f trial

N 110/565

  09 '. (2.! F ...; 7.7ssa ic m pa rat if

"19 1

91 1.6 the. "39 92" l 2. +43

LJ "+ 3

93 "22 O 32

94Po10. "L" + 5.5Test ccq) aratif

"192.4" + 12.4

96.22 "" + 9.2

  ## EQU1 ## Table 11: Lf) 0%

Table 12:

  "" COMPOSITION t CANTILL.ON TEST Test - N ° PA, MB Alliaw ajoeuté TZy FbricatUon at the same time 3ll NN% wt% Type wt% Apri CnitiOns T (OC t (Min> r. KJ / m2 kJ / 2 112 * PO - K XDB Neomat 230 15 - 5.9 17.5 N 3i0 / 565

  113 "2 _, 8PEX 1" 0 "2 O - 1 8.8 20.5

114 "21 1.8" 10 ± 13.4 36.6

115. "1.6 2" 20

  116 'Po 1 - - - 2.1 3.4 117 * "- - PEX 10" l 8 - 1.7 2.7

118 "21 1.8" 10 ... + 5.1 11.7

119. "1.6" 20 + 5.5 0.5

"2" 2.7 "10" + 7.0 16.9

  the Corparative Test% O rv% 0 mi C ('o

Table 13:

  TestCMCSITIGN TUBE EOtAN17 = 1 T E S T

  N PA MB has d 1 2 3 4 te dsinflectionJ Aerir -

  - - Incentive heating% N N% oidsm t / _, c C T (Oc) t (Min) Appr. the value of __ N% dri /. C Mn _________ face 121 5 - - 40 190 210 2. 3230 15 _ not smoothTest ccmuxur-t if '

122 30 1.3 + "

123 "19 2.0 '" "" +

124 "12 3.3 60 200 215 + ,, re = o_.t

13.3.4

  8 30 1.3 60 190 210 2.3230 15 + ouirugueuse 126 8 19 2.0 40 200 215 2. 3230 15 + ouirueuo

127 20 "" "" "

"21 225.

  129 5 * 19 2.0 40 190 210 4.0230 15 + not smooth

"22" "+

Lnl OI C \ 8 1-i ei

Table 14:

  cpEssaioltMN TVBES EOWTULX4B T 'IS PAÂ' 2 N fi_ Chau & d i, nc1 2lchatud N Nopis m t M Ouf r (C 'nT (' C1 t (M4n) Appraisal of N °.% weight_ _t__ __. - surface .. .... _ l131Po 5 -, 6.3 1 40175 180 3.7230 15 - smoothTest coCmXrawt i 132. 21 1.0 "180 190 3.6" + n

133 2.0 "" 3.5 +

13 4 "27"

  * 134, 1, 12.7: ",,,.,., +. 136 "21 1.00 t '37 +

137 O2.0 "...." ...., .. + -

  1 3 B * "". 5 O0 * "." "" "", - + - * -

138 0. 54

139 4.72 .. - ..

  Po 10- - 6.3 1 40170 170 3.9230 15 SmoothCollustriT trial

141 21 1.00 3.0

  142 ... 2.0.n "" 3. 2 ± - "143 2.24" n n + 144 "n 3.00 3.1" +

_ ,,, + _ _. '

I, 'o Ni rt'% Ln 0%

Claims (28)

-REVENDICATIONS   Process for the preparation of molded bodies made of thermoplastic polyamides which have, in comparison with polyamide starting materials, improved mechanical properties and high dimensional stability under heat, characterized in that polyamide is added before the treatment. dry a masterbatch containing at least 5% by weight of a silane of formula I: ## STR1 ## wherein n = O, 1, or 2, Z is a residue inert organic, Y is a bivalent, silicon-bonded organic radical which contains a functional group which can react with the amino groups and / or carboxyl groups and / or amide groups of the polyamide chain with formation of a chemical bond, and A is a hydrolysable residue in the presence of moisture, the remains appearing several times can also be bonded together, the polyamide mixture and master mixture are melted, the melt is thoroughly homogenized (mixed), and then ap In the usual processes of thermoplastic processing, it is molded into molded bodies, and these are subjected beforehand to natural ambient humidity or to a short packaging. duration in the water.   2. Process according to claim 1,   characterized in that, as support   masterbatch, a thermoplastic containing open pores. 259,536?   3. Method according to claim 2, characterized in that a polyamide is used as thermoplastic containing open pores.   4. Process according to claim 2, characterized   terized in that it is used as thermoplastic   a polyolefin containing open pores.   5. Process according to claim 3, characterized in that a polyamide 12 or 11 containing pores is used as a masterbatch. open.   6. Process according to claim 1, characterized in that the carrier mixture is used   master a thermoplastic copolyolefin.   7. Process according to Claim 6, characterized in that the carrier mixture is used   master a block polymer containing polybutadiene.   Process according to Claim 7, characterized in that a polymer containing styrene blocks and butadiene.   9. Process according to claim 8, characterized in that it is used as carrier-mixture   master a triblock polymer of styrene and butadiene.   Process according to Claim 1, characterized in that the carrier mixture is used   master a mixture designated by ABS or MABS.   11. Process according to claim 6, characterized in that a styrene / ethylene-butene / styrene block polymer is used as a masterbatch. 12. Process according to claim 6, characterized in that a thermoplastic copolyolefin of ethylene-propene, ethylene-butene or ethylene-hexene composition is used as the master-macerator.   ethylene-octene, ethylene-butyl acrylate, ethylene-   ethyl acrylate, ethylene vinyl acetate, ethylene   propylene-monomer diene (EPDM), or a mixture of these copolyolefins. Process according to claim 1, characterized in that a core-and-cover polymer having a crosslinked core.   Process according to Claim 13, characterized in that a core-and-cover polymer having a butadiene-containing cross-linked nucleus and / or acrylic or methacrylic acid ester and / or or styrene and / or acrylic nitrile.   15. Process according to claim 14, characterized in that a core-and-cover polymer having a shell of acrylate or methyl methacrylate is used as a masterbatch.   and / or styrene and / or grafted acrylic nitrile.   16. Process according to claim 14, characterized in that a core-and-cover polymer is used as a masterbatch which contains other olefin comonomers in the core and / or the cover. 17. Process according to claim 14, characterized in that a core polymer with a designated cover is used as the master support-mix.   commercially under the name of methacrylate-butadiene-   styrene (MBS), methacrylate-acrylonitrile-butadiene-   styrene (MABS), acrylonitrile-butadiene-styrene (ABS), or pure acrylate.   18. Process according to claims 6 and 13,   characterized in that the polymer is present in finely divided form (powder, grains, particles of diameter less than 1 mm).   19. Process according to claim 1, characterized in that a silane is used which contains, in the organic radical Y, an epoxide group, isocyanate,   aromatic ester, or acid anhydride.   20. Process according to claim 19, characterized in that the silane contains, as a hydrolysable group, the groups -OCH3, OCH2-CH3, -Oc2H4-OCH3 or -O-CO-CH3.   21. Process according to claim 1, characterized in that the silane is added in a concentration ranging from 0.1 to 5% by weight, relative to polyamide.   22. Process according to claim 1, characterized in that a linear aliphatic homopolyamide such as PA 12, PA 11, PA 6, PA 6.9, PA 6.12, PA 6.6, an elastomeric polyamide or an amorphous polyamide is used as polyamide. for example, the polyamide obtained from trimethylhexamethylenediamine and terephthalic acid, a partially crystalline homopolyamide or copolyamide, for example obtained from metaxylylenediamine and adipic acid, or another   thermally transformable polyamide or copolyamide   plastic and obtained from aliphatic monomers,   cycloaliphatic, aromatic, or hetero-aromatic   atoms. Process according to claim 1, characterized in that the polyamide contains at least 10, and preferably at least 30 amino groups in the form of   functional groups -NH- or -NH2.   Process according to claim 1, characterized in that the polyamide is dried to a maximum water content of less than 0.03% by weight, in that it is introduced into absence of moisture, in a melting and homogenizing unit, mixing with the master batch can be carried out before introduction into the melting unit, directly into the feed hopper, or only into the melt the polyamide and the masterbatch are melted and mixed thoroughly, in which operation the Y group reacts with the polyamide, and then the melt is subjected to a shaping process, for example method of extrusion or injection molding, and then exposing the molded body to the surrounding normal atmosphere, or, when used very quickly, to a packaging short term in water.   25. Process according to claim 24, characterized in that the mixture of polyamide and masterbatch is melted in an extruder, and then the treatment of this mixture is carried out according to   an extrusion or injection molding process.   26. Process according to claim 24, characterized in that the polyamide is melted,   and that a continuous proportion of   of the master batch in the polyamide dry melt, after which homogenisation is carried out   and the reaction between the polyamide and the silane.   27. Process according to claim 24, characterized in that the polyamide is dried to   obtain a water content of less than 0.02% by weight.   28. Molded bodies manufactured in accordance with one of the 1 to 27.